Heterocyclic stilbene azo dyestuffs



Patented Apr.23, 1946 L 2,399,065

HETEROCYCLIC STELBENE AZG DYESTUFFS Max Schmid, Riehen, and Eduard Moser, Basel, Switzerland, assignors to the firm Society of Chemical Industry in Basia Basel, Switzerland =No Drawing. Application March 24, 1943, Serial No. 480,381. In Switzerland March 6, 1942 8 Claims. (Cl. 260152) The present invention relates to dyestuffs of stuff which contains at least once an atom grouphe e ral for ula 7 ing which enables it to yield complex metal com- KIIIOOH SOaH S0311 which are valuable products. In this general for- 10 pounds These new dyestuffs are characterized mula R. stands for the radical of a compound havby a pronounced affinity for 0611111056 or regenerp keto group capable of updergomg f i ated cellulose, for example for textile materials tron, K stands for a connecting link consisting of the radical of a six membered heterocycnc consisting of or containing such materials, for incompound m C t t least t d t 15 stance mixtures of cotton and artificial fibers more than three mobile halogen atoms and in from regenerated cellulose and regenerated cellu-V which at least two halogen atoms have been ex- 1055 delustred by inorganic pigments respectively,

changed for the or mixtures of wool and such artificial fibers. The

20 new dyestuffs dye these materials greenish yellow groups the heterocyclic ring of the heterocyclic to reddish yellow tints. The fastness to light and compound being composed of three to four carthe wet fastness properties of the dyeings can be bon atoms and three to two nitrogen atoms, not essentially improved by a fter tr atm t with more than two nitrogen atoms being adjacent to one another, and at least two and not more than metal especlany copper salts Thls metam three carbon toms of the hetero ring being zatiOl'l can be efiected Simultaneously With dyeing. ed to mobile halogen atoms, B stands for a con- In many cases it may be appropriate to produce necting link consisting either of the radical ofa the metal Compounds of the dyestuffs as Such-and heterocyclic compound as explained for K or of I t 30 to use the metalliferous products for example like a 0-0 group, and

i l-z V I substantive dyes. H The new dyestuffs can be illustrated by the folstands for the radical of a yellow aminoazo-dyelowing characteristic representatives:

1 (3H3 (3H3 i O=N H000 1100c Kl l W t \i I r r G -rt 0 H N N N 1* H o a -SOaH 503E r "t II CH5 CH3 sols 1 J N/ F1000 H N H NOSOaH cos NC C1 I GHOH 0 o1lI- -N 0 a z u 1 J it Q l I u 0 H S0311 S0311 N H O From these formulas it is obvious to the exin which R has the above given significance, and then with a second mol of a yellow aminoazodyestuff which is capable of yielding complex metal compounds. This yellow aminoazo-dyestufi can therefore be constituted like the already mentioned aminoazo-dyestufi of the, formula (IJOOH however, it may be also quite different therefrom. The capability of the yellow aminoazodyestuff to form complex metal compounds may be due for example to the presence of an aromatically bound hydroxyl group which stands in ortho-position to a carboxyl group. If mobile halogen atoms are still contained in the discoondary condensation products thus obtained,

they are reacted preferably with compounds having mobile hydrogen atoms, such as aniline, monomethylaniline, methylamine, monoethanolamine, and the like.

However, one may also proceed in a different manner, by starting for example from i-amino- 4'-nitrostilbene-2:2'-disulfonic acid, condensing it to a so-called primary condensation product with a heterocyclic compound containing at least two mobile halogen atoms, causing the condensation product to react with one mol of an aminoazo-dyestufl of the general formula COOH wherein R has the above given significance, reducing the remaining-nitr c group to an amino group and coupling the aminoazo-dyestufi thus formed of the formula coon soin in which R and K have the above given significance, with 1 mol of a yellow aminoazo-dyestufi which is capable of forming complex metal compounds with the aid of phosgene or a heterocy- S osH .ascaoec or it may correspond to the already explained formula RN=NQNH2 or be a derivative of salicylic acid.

The order of succession may also be reversed by linking first 4-amino-4'-nitrostilbene-dlsu1- fonic acid with the aid of phosgene or a heterooyclic compound containing mobile halogen atoms of the kind of cyanuric chloride, with the yellow aminoazo-dyestufi which is capable of forming complex metal compounds, and when the reduction is complete, effecting the condensation with the dyestuff of the formula COOH Finally, any halogen atoms which may still be present can be reacted with compounds having mobile hydrogen atoms, for instance aniline, para aminoacetanilide, monomethylaniline, methylamine, monoethanolamine, and the like. In the manufacture of the new dyestufls it is of course also possible to proceed in such a manner that first of all 4-amino-4'-nitrostilbenedisulfonic acid or 4:4'-diaminostilbene-disulfonic acid is linked with the aid of phosgene or a heterocyclic compound containing at least two mobile halogen atoms with l or 2 mole. of a 1:4-diaminobenzene-Zi-carboxylic acid, dior tetrazotizing the condensation product thus obtained, uniting it with azo-components having keto groups capable of undergoing enolisation, then reducing the nitro group which may still be present to the amino group and finally coupling the aminoazodyestufl thus obtained in the indicated manner with a yellow aminoazo-dyestufi which is capable of forming complex metal compounds,

The dyestufis themselves of the general formula coon RN=N NH:

may be prepared inter alia in such a manner that an anthranilic acid nitrated in para-position to the amino group is diazotized and coupled with a compound which thanks to the presence of a keto group capable of undergoing enolisation can be united with diazo compounds to form azo compounds. Such compounds are for example acetoacetic ester derivatives such as arylides of acetoacetic acid or the pyrazolones which are obtained by condensing hydrazines with aceto-acetic ester. Such pyrazolones are for instance B-nlethyl- 5-pyrazolone and l-phenyl-3-methy1-5-pyrazolone and its derivatives substituted in the benzene nucleus for example by halogen atoms and sulfo clic compound containing at least two mobile halogen atoms which behaves similarly. Here, too, the yellow aminoazodyestufi may be a dyegroups. Further may be used the pyrazolones from other p-ketocarboxylic acid-esters, such as for example oxalacetic ester and hydrazines, or also other products, such as malonic acid or barbituric acid derivatives, for instance the barbituric acid itself or further products such as benzoylacetone 0r dihydroxyquinoline.

Heterocyclic compounds corresponding to the radical K are for example products such as cyanuric chloride, cyanuric bromide, l-phenyl-3z5- dichlorotriazine, 1 methyl-3 :5-dichlorotriazine, dichloroquinazoline, tribromopyrimidine and the like, that is to say heterocyclic' compounds con taming mobile halogen atoms of the kind of cyanuric chloride.

As yellow aminoazo-dyestuff containing still an atom grouping which is capable of forming complex metal compounds there may also be used, besides the already mentioned monoazo-dyestuffs of the formula (IJOOH while stirring well, a solution of. 18.4 parts of cyanuric chloride in little acetone. The whole is stirred for about 1 hour and the acid which becomes free is neutralized by the addition of sodium carbonate.

The diprimary condensation, product of the formula is then formed as a light yellow precipitate.

26 parts of the aminopyrazolone-azo-dyestufi of the formula COOH which has been obtained as described above are and the like.

The following examples illustrate the invention, but are not to be regarded a limiting it in any way, the parts being by weight:

Example 1 18.2 parts of 5-nitro-2-amino-lrbenzoic acid are dissolved as ammonium salt or sodium salt, the solution is mixed with '7 parts of sodium nitrite and indirectly diazotized by pouring the mixture into 40 parts of hydrochloric acid of specific gravity 1.15 and ice. When diazotization is complete, the diazo paste is added to a solution containing 10 parts of 3-methyl-5-pyrazo1one and 30 parts .of sodium carbonate in 100 parts of Water.

When coupling is complete the whole is heated, salted out and the dyestufi is suction-filtered.

The moist filtrate is introduced into about 100 parts of water and mixed at 6065 C. with a filtered solution of 36 parts of crystallized sodium sulfide in about 50 parts of warm water. The mixture is further stirred for about 3 hours at 60 0., and then allowed to cool, the reduced dyestufi is precipitated with acid, filtered and purified by redissolving from dilute sodium carbonate solutlon. A diprimary condensation product from 1 equivalent of 4:4'-diaminostilbene-2 :2'disulfonic acid and 2 equivalents of cyanuric chloride is prepared as follows:

18.5 parts of 4: l-diaminostilbene-2:2-disulionic acid are dissolved .as neutral sodium salt in about 500 parts of water and cooled to 0 C. by addition of ice. To this solution is added,

added to the mixture as neutral sodium salt in about 1200 parts of water. The solution is slowly heated to 40 C. and this temperature is maintained for 4 hours while slowly and constantly adding 16.8 parts of sodium bicarbonate for neutralizing the acid which becomes free. The disecondary condensation product from J. equivalent of diaminostilbene, 2 equivalents of cyanuric chloride and 2 equivalents of the aminopyrazolone-azo-dyestuff is temporarily dissolved and partially precipitated when the condensation is complete.

When the condensation is complete, the reaction mixture is boiled for 2 hours in a reflux apparatus after addition of 30 parts of aniline for the purpose of reacting the two remaining halogen atoms of the dyestuff. The diternary condensation product which has been formed corresponds to the above Formula I. It is precipitated with common salt after addition of sodium carbonate, suction-filtered, dried and ground.

When dry, the dyestufi is an orange powder dissolving in dilute alkalies to a yellow-orange to orange solution and dyeing cotton or regenerated cellulose orange-yellow tints which when treated or after-treated in the bath with copper are rendered excellently fast to washing and light.

The same dyestuffs can be obtained when condensing first of all 1 mol of cyanuric chloride with 1 mol of the amino-pyrazolone-azo-dyestufi, then coupling 2 mols of the primary condensation product thus obtained of the formula II OOOH' s i I N=o H N with 1 mol of diaminostilbene-disulfonic acid and finally reacting the last halogen atoms with aniline, as indicated above.

The same products can be also obtained when starting from nitroaminostilbene disulfonic acid and suitably adapting the order of succession of the various operations to the starting material.

When replacing 3-methyl-5-pyrazolone in this example by the following pyrazolones: E-pyrazolone-B-carboxylic acid, 1-pheny1-3-methyl-5- pyrazolone, 1- (4-sulfo) -phenyl-3-methyl-5-pyrazolone or other 1-phenyl-?l-methyl-5-pyrazolones r 1-phenyl-5-pyrazolone-3-carboxylic acid substituted in the phenyl nucleus, there are obtained analogous products which when containing still sulfo groups in the phenyl nucleus of the pyrazolone derivative, like the dyestufi from 1-(4'-sulfo) -pheny1-3-methyl-5-pyrazolone, can be used in the form of their copper compounds as direct dyestuffs. The conversion into copper compounds takes place in a manner known in itself, for example by treating the dyestufis with a copper sulfate solution mixed with an excess of ammonia.

Example 2 40 parts of 4-amino-4'-nitrostilbene-2:2-disulfonic acid are dissolved in about 200 parts of water with addition of caustic soda solution in such a manner that the solution obtained is neu-i CHa tral to litmus. The solution is cooled to 0 C. by addition of ice and a solution of 20 parts of cyanuric chloride in 150 parts of acetone is added while stirring. Stirring is continued for 1 hour, the acid which becomes free being neutralized with sodium carbonate solution.

A neutral solution of the reduced dyestuii obtained according to Example 1 from 26 parts of diazotized 5-nitro-2-amino-1-benzoic acid and 3-methyl-.5-pyrazolone in about 200 parts of water of 50 C. is then added to the mixture. This is heated to 40 C. and maintained at this temperature for about 4 hours, the acid which becomes free being neutralized by addition of an acid binding agent such as sodium carbonate or sodium bicarbonate. For the purpose of saturating the third chlorine atom in the cyanuric chloride, the mixture is boiled for about 2 hours after addition of 30 parts of aniline, and the condensation product of the probable formula coon" sit ate stufi is redissolved from dilute sodiumtcarbonate solution. The reduced dyestufi. is dissolved in water and treated at 40-4? C. with pho sgene until practically no amino group can be detected. The precipitated dyestuff corresponds to the Formula V of the introduction. When dry it is a red-brown powder which dissolves in dilute alkalies to orange to red orange solutions and dyes cotton fast red yellow tints which become faster to washing and light by after-treatment with agents yielding copper on the fiber or in the dyebath. Analogous dyestuffs having similar properties are obtained by replacing the 3 methyl-5- pyrazolone by pyrazolones phenylated in 3- or l-position or by pyrazolones as well as by 5- or 3-pyrazolones substituted in the phenyl radicals.

The pyrazolone dyestuffs in this or the previous examples can be replaced by such dyestuffs which areobtainedby coupling diazotized nitro-' Example 3 79.9 parts of the reduced dyestufi obtained according to Example 2 of the formula SOaH S t N HH are condensed in usual manner at 0 C. with 18.4 parts of cyanuric chloride. When the condensation is complete, a warm solution of 28 parts of the sodium salt of 4-amino-4'-hydroxyazobenzene-3-carboxylic acid is added. The temperature is raised to about 40 C., the temperature is maintained for about 4 hours, the acid which is liberated by the condensation being neutralized by addition of sodium bicarbonate. For the purpose of saturating the third chlorine atom of the cyanuric chloride the condensation product is boiled for about 2 hours in the presence of aniline. The dyestufl obtained corresponds to the Formula VI of the introduction and is salted out and isolated in the usual manner. When dry it is a yellow orange powder which dissolves in dilute alkalies to orange to red orange solutions and dyes cotton and regenerated cellulose yellow tints which become excellently fast to washing and light when after-treated with agents SOaH SOzH

yielding copper in substance on the fiber or in y the dye-bath. When replacing the 3-methyl-5- pyrazolone in this example by other pyrazolones or the aminoazo-benzene-salicylic acid by other yellow a'minoazo-dyestulfs which are capable of yielding complex compounds with metals, analogous products'are obtained which produce valuable dyeings on cotton when treated with agents acid, suction-filtered, and if necessary the dyeyielding metal.

aseaoee' Erample 4 Example 1 and 2 parts of sodium carbonate. The

bath is heated to 9095 C. during A2 hour, 30 parts of crystallized sodium sulfate'are added and dyeing is continued for n hour at this temperature. A solution, neutralized with caustic soda solution, of 2 parts of crystallized copper sulfate and 2.5 parts of tartaric acid in 100 parts of water is then added to the dye-bath and the cotton is treated therein for /2 hour at about 95 C., after which it is rinsed as usual and dried. The cotton is dyed fast yellow tints.

As indicated in the introduction, the dyestuffs of the present invention may also be used for dyeing mixed fabrics, for example mixtures of wool and viscose artificial wool. In such cases dyeing is advantageousl conducted in a neutral bath in presence of sodium or potassium chromate.

What we claim is:

1. The dyestuffs corresponding in the free form to the general formula RN=N I S0311 S0311 H coon wherein R stands for the radical of a compound having a keto group capable of undergoing enolisation, K stands for a connecting link consisting of the radical of a six-membered heterocyclic compound,'the heterocyclic ring of which is composed of three to four carbon atoms and three to two nitrogen atoms, not more than two nitrogen atoms being adjacent to one another, the

groups'adjacent to K being attached to carbon atoms of the hetero-ring thereof, and one carbon atom of the latter bearing a substituent selected from the group consisting of a halogen atom and the radical obtained by the reaction of this halogen atom with a primary amine, B stands for a connecting link selected from the group consistwherein it stands for the radical of a keto group capable of undergoing enolisation, K stands for a connecting link consisting, of the radical of a six-membered heterocyclic system containing a 'heterocyclic six-membered ring consisting of carbon and nitrogen atoms, of which at least three and not more than four are carbon atoms and at least two and not more than three are nitrogen atoms, not more than two nitrogen atoms being linked with each other, said heterocyclic sixmembered ring containing at least twice and not more than three times the atom grouping to the carbon atoms or two of which the adjacent groups of the above formula are connected, the atom grouping not connected to the said III-z H stands for the radical of a yellow aminoazo-dyestuff, which products form yellow to brownpowders the alkali salts of which dissolve in Water to yellow solutions.

3. The dyestuffs corresponding in the free form to the general formula COOH I /N\ /N\ i-r rt Cw W l -r H N N H. V H N N n C/ S0311 80311 \G% ing of the radical of a heterocyclic compound as explained for K and of the 0:0 group, and

stands for the radical of a yellow aminoazo-dyestuff, which prducts form yellow to brown powders the alkali salts of which dissolve in water to yellow solutions.

2. The dyestuffs corresponding in the free form to the general formula COOH S0311 $0311 wherein R stands for the radical of a compound having a keto group capable of undergoing enolisation,

4. The dyestufls corresponding in the free form to the general formula COOH to the pyrazolone nucleus in 4-position, and :1: stands for a member of the group consisting of 7 coon CH M as which products form yellow to brown powders the alkali salts of which dissolve in water to yellow solutions,

N: l nooc c- -N=N N-G/ \C-N on=on ti it it OK EEO 80:11

5. The dyestufis corresponding in the free form to the general formula COOH wherein Py stands for the radical of a 5-pyrazolone compound, the adjacent azo-group is linked N i Q Qi-t w s r t t m m H t Ht a halogen atom and the radical obtained by the reaction of this halogen atom with primary amines containing not more than 8 carbon atoms;

which products form yellow to brown powders the alkali salts of which dissolve in water to yellow solutions.

6. The dyestuff corresponding in the free form to the formula 7. The dyestufi corresponding in the free form to the formula coon COOH

8. The dyestuff corresponding in the free form to the formula MAX SCHMID. EDUARD MOSER. 

